CN102977365A - Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof - Google Patents
Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof Download PDFInfo
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- CN102977365A CN102977365A CN201210514313XA CN201210514313A CN102977365A CN 102977365 A CN102977365 A CN 102977365A CN 201210514313X A CN201210514313X A CN 201210514313XA CN 201210514313 A CN201210514313 A CN 201210514313A CN 102977365 A CN102977365 A CN 102977365A
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- annular lactone
- ethoxy carbonyl
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Abstract
The invention discloses a method for copolymerizing diazoacetate and cyclic lactone. The specific preparation method comprises the following steps of: reacting the diazoacetate and the cyclic lactone as monomers for a period of time under microwave irradiation in the presence of an initiator and under the condition of inert gas protection, thereby obtaining the polymer. The method is free of catalyst and solvent, simple and convenient to prepare, easy in parameter control and fast in reaction, and the prepared polymer is large in molecular weight and a brand new path is provided for the copolymerization reaction of the cyclic lactone and free radicals. The polymer prepared by the method provided by the invention is expected to be widely applied to fields of rubber, plastics and the like.
Description
Technical field
The present invention relates to the method for a kind of diazonium acetate and annular lactone copolymerization.
Background technology
Utilize diazonium salt to be called the Cabbeen polymerization as monomer and the polyreaction of sloughing nitrogen.This reaction is the reaction that the class of relying on organo-metallic catalyst to carry out obtains having the novel texture polymkeric substance.In the reaction process, organo-metallic catalyst and diazonium salt monomer form the generation that title complex has promoted leaving away of nitrogen and metal carbene intermediate.The characteristics of this reaction are the polymkeric substance that has obtained a kind of brand new, on main chain, can be connected to modification group on each carbon atom.The ring-opening polymerization of the annular lactone under the microwave exposure (Microwaves) is the common polyreaction of a class, and its advantage is: reaction is quick, and the polymericular weight that obtains is large, and dispersion coefficient is low.But the ring-opening polymerization of Cabbeen polymerization and annular lactone all needs to use organo-metallic catalyst, has caused the destruction of the wasting of resources and environment.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and the terpolymer of a kind of diazonium acetate, ethoxy carbonyl Cabbeen and annular lactone is provided.
The present invention also provides the preparation method of the terpolymer of diazonium acetate, ethoxy carbonyl Cabbeen and annular lactone.
The present invention for the technical scheme that provides is provided is: the terpolymer of a kind of diazonium acetate, ethoxy carbonyl Cabbeen and annular lactone, and concrete general formula is as follows:
Wherein, x, y, z refer to any greater than 0 integer; N refers to that 0 reaches above integer; R
1And R
2Refer to any group, comprise a kind of in alkane, alkene, aromatic hydrocarbons or the halogen.
The preparation method of the terpolymer of a kind of above-mentioned diazonium acetate, ethoxy carbonyl Cabbeen and annular lactone, be specially: in the presence of rare gas element and initiator, diazonium acetate and annular lactone are mixed with arbitrary proportion, through behind the microwave exposure, with the product process reprecipitation that obtains, remove the terpolymer that organic solvent obtains diazonium acetate, ethoxy carbonyl Cabbeen and annular lactone.
Initiator can be in alcohols, primary amine, secondary amine or the acids any, is a kind of in phenylcarbinol, Virahol or the vinylcarbinol as a kind of preferred initiator.
The microwave power of microwave exposure 200 watts and more than, the microwave time is 3min ~ 5h.
Reaction monomers diazoacetic acid ester synthesis among the present invention is the method in the reference literature, namely under 0 ~ 10 ℃ environment, with the 0.1mol glycine ester hydrochloride, 20ml distilled water, 0.0015mol sulfuric acid and 30ml1, the 2-ethylene dichloride joins in the there-necked flask, after the cooling, slowly add the aqueous solution of the Sodium Nitrite of 15ml 0.12mol, maintain the temperature at below 10 ℃, stirred 2 hours, reaction system is transferred in the separating funnel.Tell organic phase, water is used respectively 1 of 8ml, and the extraction of 2-ethylene dichloride merges organic phase, with the saturated sodium bicarbonate solution washed twice of 10ml, uses anhydrous sodium sulfate drying.Obtain diazonium acetate through underpressure distillation.
The purifying of reaction monomers annular lactone monomer: annular lactone monomer and hydrolith were at room temperature stirred 48 hours, and underpressure distillation obtains purified product under vacuum condition.
Preparation method of the present invention is expressed as follows with equation:
Wherein, x, y, z refer to any greater than zero integer, n nulling and above integer thereof, R
1, R
2Refer to any group, comprise alkane, alkene, aromatic hydrocarbons, halogen etc., wherein compound R
2H is initiator.
The outstanding feature of method provided by the present invention is:
1. the preparation of reaction monomers diazonium acetate is simple and convenient, and annular lactone is simple and easy to.
2. first the Cabbeen polymerization is introduced the microwave reaction system, initiative realization the copolymerization of Cabbeen polymerization and ring-opening polymerization.
3. the method is simple and convenient, and parameter is controlled easily.
4. the method does not need to use organo-metallic catalyst, avoids with an organic solvent in the reaction process.
5. the ring-opening polymerization with Cabbeen polymerization and annular lactone of the method initiative is linked together by microwave reaction, and a kind of green is provided, and is convenient, rapidly synthesis path.
6. the polymkeric substance that obtains of the present invention is a kind of brand-new material, contains azo group on the main chain of polymkeric substance, can be applied to research and the preparation of optical material.
7. polymkeric substance is polyester, has good degradability, is a kind of material of environmental protection.
8. polymkeric substance is the polymkeric substance of amorphous state, and second-order transition temperature is higher.
Description of drawings
Fig. 1 is the ethyl diazoacetate of phenylcarbinol initiation and the hydrogen nuclear magnetic spectrogram of 6-caprolactone copolymerization product, and a ~ f among the figure is the position of hydrogen atom in the nuclear magnetic spectrogram.
Embodiment
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
Under argon shield, the phenylcarbinol of 0.0001mol is as initiator, and the 6-caprolactone of 0.01mol ethyl diazoacetate and 0.01mol was through 200 watts of microwave exposures 120 minutes.The product that obtains is through tetrahydrofuran (THF)/methyl alcohol reprecipitation.Vacuum is removed organic solvent can obtain polymkeric substance.The molecular weight that obtains polymkeric substance is 36100, productive rate 24.61%, nitrogen content 1.38%.
Embodiment 2
Under argon shield, the phenylcarbinol of 0.0001mol is as initiator, and the δ-valerolactone of 0.01mol ethyl diazoacetate and 0.01mol was through 200 watts of microwave exposures 120 minutes.The product that obtains is through tetrahydrofuran (THF)/methyl alcohol reprecipitation.Vacuum is removed organic solvent can obtain polymkeric substance.The molecular weight that obtains polymkeric substance is 1500, productive rate 29.45%, nitrogen content 4.17%.
Embodiment 3
Under nitrogen protection, the phenylcarbinol of 0.0001mol is as initiator, and the gamma-butyrolactone of 0.01mol ethyl diazoacetate and 0.01mol was through 200 watts of microwave exposures 300 minutes.The product that obtains is through tetrahydrofuran (THF)/methyl alcohol reprecipitation.Vacuum is removed organic solvent can obtain polymkeric substance.The molecular weight that obtains polymkeric substance is 2100, productive rate 26.20%, nitrogen content 5.54%.
Embodiment 4
Under argon shield, the Virahol of 0.0001mol is as initiator, and the 6-caprolactone of 0.01mol diazoacetic acid methyl esters and 0.01mol was through 300 watts of microwave exposures 60 minutes.The product that obtains is through tetrahydrofuran (THF)/methyl alcohol reprecipitation.Vacuum is removed organic solvent can obtain polymkeric substance.The molecular weight that obtains polymkeric substance is 20100, productive rate 28.30%, nitrogen content 1.74%.
Embodiment 5
Under argon shield, the vinylcarbinol of 0.0001mol is as initiator, 0.02mol diazonium acetate (R
1=Ph) and the 6-caprolactone of 0.03mol, through 400 watts of microwave exposures 3 minutes.The product that obtains is through tetrahydrofuran (THF)/methyl alcohol reprecipitation.Vacuum is removed organic solvent can obtain polymkeric substance.The molecular weight that obtains polymkeric substance is 15800, productive rate 24.30%, nitrogen content 1.94%.
Claims (6)
1. the terpolymer of a diazonium acetate, ethoxy carbonyl Cabbeen and annular lactone, concrete general formula is as follows:
Wherein, x, y, z refer to any greater than zero integer; N nulling and above integer; R
1And R
2Be any group.
2. the terpolymer of a kind of diazonium acetate according to claim 1, ethoxy carbonyl Cabbeen and annular lactone is characterized in that: described any group comprises a kind of in alkane, alkene, aromatic hydrocarbons or the halogen.
3. the preparation method of the terpolymer of a diazonium acetate as claimed in claim 1, ethoxy carbonyl Cabbeen and annular lactone, it is characterized in that, be specially: in the presence of rare gas element and initiator, diazonium acetate and annular lactone are mixed with arbitrary proportion, through behind the microwave exposure, with the product process reprecipitation that obtains, remove the terpolymer that organic solvent obtains diazonium acetate, ethoxy carbonyl Cabbeen and annular lactone.
4. the preparation method of the terpolymer of a kind of diazonium acetate according to claim 3, ethoxy carbonyl Cabbeen and annular lactone is characterized in that: described initiator is a kind of in alcohols, primary amine, secondary amine or the acids.
5. the preparation method of the terpolymer of a kind of diazonium acetate according to claim 4, ethoxy carbonyl Cabbeen and annular lactone is characterized in that: described initiator is a kind of in phenylcarbinol, Virahol or the vinylcarbinol.
6. according to claim 3 or the preparation method of the terpolymer of 4 described a kind of diazonium acetates, ethoxy carbonyl Cabbeen and annular lactone, it is characterized in that: the microwave power of described microwave exposure 200 watts and more than, the microwave time is 3min ~ 5h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210514313.XA CN102977365B (en) | 2012-12-03 | 2012-12-03 | Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof |
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| CN201210514313.XA CN102977365B (en) | 2012-12-03 | 2012-12-03 | Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof |
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| CN102977365A true CN102977365A (en) | 2013-03-20 |
| CN102977365B CN102977365B (en) | 2014-06-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319709A (en) * | 2013-07-04 | 2013-09-25 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN104311822A (en) * | 2014-10-31 | 2015-01-28 | 武汉大学 | Carbene-diazo compound-olefine aldehyde terpolymer and application of carbene-diazo compound-olefine aldehyde terpolymer as bidirectional conversion fluorescent material and anti-cancer drug |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348842A (en) * | 1992-03-06 | 1994-09-20 | Hoechst Celanese Corporation | Method for producing positive photoresist image utilizing diazo ester of benzolactone ring compound and diazo sulfonyl chloride |
| CN1339512A (en) * | 2001-09-13 | 2002-03-13 | 武汉大学 | Polyhydrocarbon oxygen carbonyl carbene and its preparing method and use |
| CN1388144A (en) * | 2002-06-07 | 2003-01-01 | 武汉大学 | Prepn of poly (epsilon-caprolactone) |
-
2012
- 2012-12-03 CN CN201210514313.XA patent/CN102977365B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348842A (en) * | 1992-03-06 | 1994-09-20 | Hoechst Celanese Corporation | Method for producing positive photoresist image utilizing diazo ester of benzolactone ring compound and diazo sulfonyl chloride |
| CN1339512A (en) * | 2001-09-13 | 2002-03-13 | 武汉大学 | Polyhydrocarbon oxygen carbonyl carbene and its preparing method and use |
| CN1388144A (en) * | 2002-06-07 | 2003-01-01 | 武汉大学 | Prepn of poly (epsilon-caprolactone) |
Non-Patent Citations (1)
| Title |
|---|
| 肖龙强等: ""微波条件下的卡宾聚合"", 《2011年全国高分子学术论文报告会论文摘要集》, 24 September 2011 (2011-09-24), pages 86 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319709A (en) * | 2013-07-04 | 2013-09-25 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN103319709B (en) * | 2013-07-04 | 2015-06-10 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN104311822A (en) * | 2014-10-31 | 2015-01-28 | 武汉大学 | Carbene-diazo compound-olefine aldehyde terpolymer and application of carbene-diazo compound-olefine aldehyde terpolymer as bidirectional conversion fluorescent material and anti-cancer drug |
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| CN102977365B (en) | 2014-06-04 |
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